Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/12—Applications used for fibers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
  • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

• the invention relates to a polymer composition and a process for its preparation. Furthermore, the invention relates to the use of
• Polymer composition for producing films, moldings or fibers and such products containing the polymer composition according to the invention.
• plasticizer-free thermoplastic polymer composition based on starch, which is particularly suitable for blown film extrusion, flat film extrusion and suitable for injection molding of fully biodegradable products is commercially available under the trade name "BIOPLAST ® GF 106/02" from the company B10TEC GmbH & Co. KG in Emmerich (Germany).
• BIOPLAST ® GF 106/02 trade name
• biodegradable polymer compositions for example, in the publications EP 0 596 437 Bl and EP 02 203 511 Bl.
• the main applications of biodegradable polymer compositions are in the packaging and catering sector.
• Particularly relevant are biodegradable polymer compositions for the manufacture of garbage bags, carrier bags, disposable tableware (cups, cups, plates, cutlery), packaging films, bottles, fruit and vegetable trays (so-called trays),
• renewable raw materials e.g., compostable garbage bags
• fully biodegradable polymer compositions heretofore available and film products made therefrom are predominantly of polymeric materials of fossil origin, such as aliphatic-aromatic copolyesters.
• content of renewable resources e.g., starch
• Polymer compositions usually well below 50%.
• PHA polyhydroxyalkanoates
• PHAs are naturally occurring linear polyesters of hydroxy acids, which are formed by many bacteria as a reserve for carbon and energy and are deposited in the form of granules inside the cell. From the state of the art, industrial biotechnological PHA production using natural or genetically modified bacterial strains or plants is known.
• Postcrystallization of the PHA polymers following their processing into films The spherulites resulting from the postcrystallization are believed to act as impurities in the film and thus appear to significantly reduce important mechanical film properties, e.g. Elongation at break and dielectric strength, to lead.
• nucleating agents such as boron nitride (BN), talc (Mg 3 [Si40io (OH) 2 ]) and lime (CaC0 3 ) particles, cyclodextrins, polyvinyl alcohol
• Particles, terbium oxide, saccharin, thymine, uracil, orotic acid or cyanuric acid, for Use come.
• the known methods have in common that the addition of such nucleating agent accelerates nucleation and crystal growth. This is to ensure that already at
• a high crystallite density generally does not adversely affect the mechanical properties of the polymer compositions.
• nucleating agents in PHA-containing polymer compositions so far only in the field of injection molding satisfactory results.
• the addition of nucleating agents may delay the subsequent recrystallization and associated embrittlement and
• a further object of the invention was to provide a biodegradable polymer composition which has the highest possible proportion of bio-based polymers, such as starch and PHA, with simultaneously excellent mechanical properties. This object is achieved according to the invention by the polymer composition specified in claims 1 and 28, the process specified in claim 21, which in
• Total weight of the polymer composition at least the following
• Components a) from 5 to 50% by weight of destructurized starch and / or starch derivative,
• An essential feature of the polymer composition according to the invention is the combination of relatively large amounts of the bio-based polymers starch or
• Starch derivative (5 to 50% by weight) and PHA (10 to 50% by weight) with 3 to 25% by weight of polylactic acid.
• polylactic acid such as 3, 5 or 7.5 wt .-%
• similar mixtures already after 24 hours have a significantly changed compared to the freshly manufactured state mechanical profile (curing, embrittlement), which is due to the described, uncontrolled Nachkristallisation.
• PLA appears to counteract the slow post-crystallization that would otherwise occur with PHA-containing polymer compositions.
• Polymer compositions according to the invention retain their good mechanical properties even after storage of, for example, 24 h, despite PHA contents of from 10 to 50% by weight and show virtually no embrittlement.
• the effect of PLA addition is surprising since pure PLA, as a linear partially crystalline polymer itself, is relatively brittle and therefore was not expected to cause embrittlement of the PLA addition
• Polymer composition could counteract.
• the polymer composition contains, based on the total weight of the polymer composition, at least the following components: a) from 5 to 50% by weight of destructurized starch and / or starch derivative,
• films produced from the polymer composition preferably have a tensile strength according to DIN 53455 of 5 to 60 N / mm 2 , in particular of 10 to 40 N / mm 2 and / or an elongation at break according to DIN 53455 of 100 to 800%, in particular from 200 to 600 %, on.
• Polymer compositions with comparably high proportions of PHA retain the mechanical properties of the films produced from the polymer composition according to the invention during storage as much as possible.
• a precondition for the appearance of a peak in the DSC measurement is that the phase transition occurs during the measurement, that is to say when passing through the temperature program.
• an amorphous sample which crystallizes during the heating produces an exothermic peak.
• the energy conversion of the phase transition has already taken place before the beginning of the DSC measurement and then no longer generates the corresponding energy expenditure and the associated peak during the measurement.
• Crystallization peaks can usually be detected on the first heating up of freshly processed, PHA-based materials in the DSC (the sample introduced into the measuring device is still largely amorphous and crystallizes during the measurement).
• a stored over several hours / days (and recrystallized during storage) material of the same composition that peak no longer or only in attenuated form.
• the existence of crystallites in the material is due to the appearance of (endothermic) melting peaks
• films according to the invention show only a slight recrystallization within the first 24 hours after storage. This is characterized in that the size (area) of the crystallization peak measured 24
• the polymer compositions according to the invention can also be characterized in that the degree of crystallinity of a film produced from the polymer composition increases in the first 24 hours after preparation by at most 20 percentage points, in particular at most 15 or at most 10 percentage points. At a degree of crystallinity immediately after film production of, for example, 40%, an increase of 20 means
• Crystallinity Percentage points that the degree of crystallinity measured after 24 hours 60% is.
• crystallinity, degree of crystallinity and crystallinity are used in the literature as synonyms and designate the crystalline portion of a semi-crystalline solid.
• the crystallization rates given above are based on weight and not volume and are determined calorimetrically by determining the heat of fusion by fusion (cf., for example, Adolf Franck: Kunststoff- Kompendium, Vogel Buchverlag, 6th edition, chapter 3.2.4 on pages 92 and 93 or Menges et al .: Maschinenstoff ambience Kunststoffe, Hanser Verlag, 5th edition, chapter 8.2.4.2, pages 263 to 265).
• Sphotrolites are radially symmetric crystal aggregates and are typical structural units for semi-crystalline thermoplastic materials.
• the size and number of spherulites in a polymer influences the mechanical properties of the plastic.
• a disadvantage of the PHA-containing polymer compositions described in the prior art is that when they are stored
• spherulites are crystalline regions and thus birefringent, they can be detected by polarization microscopy. The appearance varies and depends on the exact polymer composition. As a rule, spherulites are recognized as circular objects and / or on the basis of the typical pattern ("Maltese cross"), whose dark bars are parallel to the polarization direction of the polarizer and analyzer of the
• Microscopes are aligned.
• Film hardness measured according to DIN EN ISO 527 a film produced from the polymer composition of the invention over the first 24 hours after film production remains largely stable.
• stable means in particular that the tensile strength increases by at most 20%, preferably at most 15%, or at most 10% or 5%.
• the tensile strength measured according to DIN EN ISO 527 remains one of the invention
• the dart drop, a measure of the dielectric strength, according to ASTM D-1709 of a film produced from the polymer composition according to the invention remains largely stable over the first 24 hours after film production.
• stable means in particular that the dart drop value decreases by at most 20%, preferably at most 15%, or at most 10% or 5%.
• the dart drop measured according to ASTM D-1709 of a film produced from the polymer composition according to the invention remains largely stable even 14 days after film production.
• polymer composition according to the invention are characterized in that the elongation at break, a measure of the elasticity, according to DIN 53455 one of
• Polymer composition produced film remains largely stable over the first 24 hours after film production.
• stable means in particular that the elongation at break decreases by at most 15%, preferably at most 10%, or at most 5%.
• the elongation at break measured according to DIN 53455, preferably remains one of the polymer composition according to the invention
• the polymer composition according to the invention according to EN 13432 is biodegradable, in particular completely biodegradable.
• the polymer composition according to the invention has thermoplastic properties.
• the polymer composition is thermoplastically processable.
• starch or starch derivative used to prepare the polymer composition according to the invention is preferably obtained from potato, maize, tapioca or rice.
• Starch derivative as used herein means modified or
• the starch derivative used is preferably starch whose free OH groups are at least partially substituted. It is a possibility
• starch derivatives are hydrophobized or hydrophilized starch, in particular e.g. Hydroxypropyl starch or carboxymethyl starch.
• the destructurized starch contained in the polymer composition of the invention was formed in the preparation of the polymer composition from native potato starch, tapioca starch, rice starch and corn starch by mechanical and / or thermal destructuring.
• the polymer composition contains from 10 to 50% by weight, based on the total weight of the polymer composition, of destructurized starch and / or starch derivative.
• the polymer composition contains from 15 to 50% by weight, preferably from 20 to 50% by weight, more preferably from 20 to 45% by weight, more preferably from 25 to 45% by weight, on most preferably 25 to 40% by weight of destructurized starch and / or starch derivative, each based on the total weight of the polymer composition.
• starch and / or starch derivative it also includes mixtures of different starches and / or different starch derivatives.
• the starch or the starch derivative is in destructurized form.
• Destructured means that the granular, crystalline structure of native starch has been completely or at least largely destroyed. This can easily be determined, for example, when viewing cross-sections in the scanning electron microscope.
• the starch phase of the polymer composition can be isolated and examined under a polarizing microscope for the presence of crystalline constituents.
• destructurized starch is to be distinguished from cases in which native starch is used merely as a filler and the granular structure of the starch is at least partially retained.
• Destructured starch may conveniently be in the form of (optionally prefabricated) plasticizer-containing thermoplastic starch (TPS) in the inventive
• the destructurized starch in the polymer composition according to the invention is preferably as free from plasticizer as possible.
• native starch is preferably homogenized together with at least one hydrophobic polymer and at a sufficiently high water content under the action of high shear forces and temperatures.
• the water is preferably removed again by drying during or at the end of the homogenization.
• the polymer composition of the present invention contains less than 5 wt%, more preferably less than 2.5 wt%, and most preferably less than 1 wt% or less than 0.5 wt% of carbon-containing plasticizers.
• these carbon-containing plasticizers are glycerol and / or sorbitol.
• Carbon-containing plasticizers are arabinose, lycose, xylose, glucose, fructose, mannose, allose, altrose, galactose, gulose, iodose, inositol, sorbose, talitol and monoethoxylate, monopropoxylate and monoacetate derivatives thereof, and ethylene, ethylene glycol, propylene glycol, Ethylene diglycol, propylene diglycol, ethylene triglycol, propylene triglycol, polyethylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3-, 1,4-butanediol, 1,5-pentanediol, 1,6- , 1,5-hexanediol, 1,2,6-, 1,3,5-hexanetriol, neopentyl glycol, trimethylolpropane, pentaerythr
• the polymer composition according to the invention preferably further contains less than about 10% by weight of low molecular weight substances and is thus substantially free from plasticizer.
• Low molecular weight substances in the context of the invention are understood to mean substances having a molecular weight of less than 500 g / mol, in particular less than 250 g / mol.
• Low molecular weight substances according to the invention are in particular water, glycerol, sorbitol and / or mixtures thereof.
• Polymer composition according to the invention less than 7 wt.%, In particular less than 5 wt.%, Preferably less than 3 wt.% or 1.5 wt.%, Based on the total composition, of low molecular weight substances.
• the polymer composition according to the invention contains from 20 to 70% by weight, preferably from 20 to 65% by weight, more preferably from 20 to 60% by weight, more preferably from 30 to 58% by weight, even more preferably from 30 to 55% by weight, most preferably from 30 to 50 wt.% Aliphatic-aromatic copolyester, each based on the Total weight of the polymer composition.
• aliphatic-aromatic copolyester preferably mixtures
• various aliphatic-aromatic copolyester comprises.
• Aliphatic-aromatic copolyesters which are biodegradable according to EN 13432 and / or have a glass transition temperature (Tg) of less than 0 ° C. are particularly suitable for the polymer composition according to the invention.
• aliphatic-aromatic copolyesters contained are also preferably thermoplastic.
• the aliphatic-aromatic copolyester a random copolyester based on at least adipic acid and / or sebacic acid. More preferably, it is a copolyester or random copolyester based on 1,4-
• Terephthalic acid derivative eg, dimethyl terephthalate DMT.
• This may in particular have a glass transition temperature (Tg) of -25 to -40 ° C, in particular -30 to -35 ° C, and / or a melting range of 100 to 120 ° C, in particular 105 to 115 ° C.
• Tg glass transition temperature
• the aliphatic-aromatic copolyester is essentially made from fossil raw materials and, according to ASTM 6866, contains less than 5% of bio-based carbon.
• the polymer composition according to the invention contains 10 to 50% by weight.
• Polyhydroxyalkanoate based on the total weight of the polymer composition.
• the polymer composition contains from 15 to 45% by weight, in particular from 15 to 40% by weight, more preferably from 15 to 35% by weight, more preferably 15 to 30% by weight of polyhydroxyalkanoate, each based on the total weight of the polymer composition.
• polyhydroxyalkanoate also includes mixtures of different polyhydroxyalkanoates.
• a particular aspect of the polymer composition according to the invention is that it may contain polyhydroxyalkanoates in an amount of 10% by weight or more, in particular also 12.5% by weight or more, preferably 15, 18, 19 or 20% by weight or more, without that the products made from the polymer composition, such as, for example, films, undergo considerable postcrystallization or embrittlement during storage.
• the polymer composition according to the invention is the ratio of
• Polyhydroxyalkanoate (this is usually biobased) to the amount of
• the amount of components c) [polyhydroxyalkanoate] present in the polymer composition is at least 20% by weight, based on the total amount of components b) and c) contained in the polymer composition [total amount of aliphatic-aromatic copolyester and polyhydroxyalkanoate]. If polyhydroxyalkanoate is mentioned here, it is so
• Polyhydroxy fatty acids containing monomers having a chain length of at least 4 carbon atoms Polylactic acid is thus e.g. no polyhydroxyalkanoate according to the invention, poly-3-hydroxybutyrate (PHB) or poly-4-hydroxybutyrate (P4HB), however, already.
• PHB poly-3-hydroxybutyrate
• P4HB poly-4-hydroxybutyrate
• Polyhydroxyalkanoate used which comprises repeating monomer units of the formula (1)
• R is an alkyl group of the formula CnHbn + i and n is a number from 1 to 15, preferably from 1 to 6.
• polyhydroxyalkanoate is selected from poly-3-hydroxybutyrate (PHB),
• Polyhydroxyalkanoate in particular PHBH, is used.
• mixtures of various polyhydroxyalkanoates containing from 10 to 20% by weight, preferably from 12 to 18% by weight, based in each case on the total amount of polyhydroxyalkanoate, give very good results.
• the polyhydroxyalkanoate is biobased and / or biotechnologically produced.
• Molecular weights M w from 70 000 to 1 000 000, preferably from 100 000 to 1 000 000 or from 300 000 to 600 000 and / or melting points in the range of 100 to 190 ° C.
• the polymer composition according to the invention contains 3 to 25% by weight.
• polylactic acid based on the total weight of the polymer composition.
• the polymer composition contains 5 to 25% by weight, in particular 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 12% by weight of polylactic acid, in each case based on the total weight of the polymer composition.
• the amount of polylactic acid is chosen such that the total amount of polylactic acid present in the
• Polymer component contained a) [starch and / or
• the polymer composition according to the invention may further comprise, as further constituent, an epoxide group-containing polymer, which is preferably an epoxide group-containing copolymer.
• an epoxide group-containing polymer which is preferably an epoxide group-containing copolymer.
• epoxide-containing polymers or copolymers are in particular those in question, the one
• Molecular weight M w of from 1,000 to 25,000, in particular from 3,000 to 10,000.
• the epoxy group-containing polymer is a glycidyl (meth) acrylate-containing polymer.
• a suitable glycidyl (meth) acrylate-containing polymer is, for example, a copolymer of (a) styrene and / or ethylene and / or methyl methacrylate and / or methyl acrylate and (b) glycidyl (meth) acrylate.
• glycidyl (meth) acrylate-containing polymer is a copolymer selected from the group consisting of styrene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate and ethylene-glycidyl methacrylate.
• glycidyl (meth) acrylate is preferably in an amount of 1 to 60% by weight, especially 5 to 55% by weight, more preferably 45 to 52% by weight, based on the total composition of glycidyl (meth) acrylate-containing
• the mixture preferably contains 0.01 to 5% by weight, in particular 0.05 to 3% by weight, more preferably 0.1 to 2% by weight of polymer containing epoxide groups, based on the total composition.
• the polymer composition according to the invention may further comprise, as further constituent, other polymers which are preferably polymers selected from the group consisting of polyvinyl acetate, polyethylene glycol, polyvinyl alcohol, chitin, chitosan, cellulose, cellulose derivatives, polyesters,
• Polydimethylaminoethyl methacrylate and mixtures thereof are those which have a molecular weight of from 1,000 to 80,000, preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000.
• the mixture preferably contains 0.1 to 5% by weight,.%, In particular 0.05 to 3% by weight, more preferably 0.1 to 2% by weight of these polymers, based on the total composition.
• polymer composition according to ASTM 6866 contains at least 50% bio-based carbon.
• the teaching of the invention allows for the first time the use of larger amounts of polyhydroxyalkanoate and starch or starch derivative in polymer compositions without adverse effects on the mechanical properties. According to the invention, therefore, a minimum content of 50% of bio-based carbon according to ASTM 6866 can be maintained even if the aliphatic-aromatic copolyester also contained in the polymer composition consists essentially of fossil
• ASTM 6866 contains less than 5%, in particular no bio-based carbon. According to a preferred embodiment, at least 90% by weight, preferably at least 95% by weight or at least 98% by weight, of the biobased carbon contained in the polymer composition according to the invention according to ASTM 6866 originates from the components a) [starch or starch derivative] and / or c) [polyhydroxyalkanoate]
• the polymer composition according to the invention can be used in addition to
• Main constituents starch or starch derivative, aliphatic-aromatic copolyesters, polyhydroxyalkanoate and polylactic acid further constituents, in particular further polymers and / or conventional additives, such as
• Processing aids plasticizers, stabilizers, anti-flaking agents,
• Antiblocking agents and / or fillers are preferably silica, talc and / or
• the polymer composition preferably contains less than 1% by weight of antiblocking agent.
• the antiblocking agents are used as fine-grained powder.
• the antiblocking agent particles have a size of less than 100 ⁇ , in particular less than 70 ⁇ , more preferably less than 50 ⁇ , more preferably less than 30 ⁇ , and most preferably less than 15 ⁇ .
• the styrene resin To prevent deterioration of important mechanical properties during storage. According to one embodiment of the invention, the
• Polymer composition no or only minor amounts (for example less than 10% by weight or less than 3% by weight, based on the total composition)
• Nucleating agents such as boron nitride (BN), talc (Mg3 [Si40io (OH) 2]) and lime (CaCC> 3) particles, cyclodextrins, polyvinyl alcohol particles, terbium oxide, Saccharin, thymine, uracil, orotic acid and / or cyanuric acid.
• the polymer composition contains less than 10 wt.% CaCC> 3 and / or less than 3 wt.% Talc, in each case based on the
• CaCO 3 and / or talc are in the
• the invention further provides methods by which it is possible to obtain the polymer compositions described above.
• the processes according to the invention comprise the following steps, wherein the individual steps can be carried out simultaneously or successively and in any order and frequency:
• Preparation of a mixture comprising, based on the total weight of the mixture, at least the following components: a) from 5 to 50% by weight of destructurized starch and / or starch derivative, b) from 20 to 70% by weight of aliphatic-aromatic copolyester,
• the method according to the invention comprises the following steps, wherein the individual steps can be carried out simultaneously or successively and in any order and frequency:
• Composition can be one-stage or multi-stage. Especially good
• Results are established in practice when the preparation of the mixture in step (i) takes place in two stages, such that first
• a polymer blend A comprising the components a) [destructurized starch and / or starch derivative] and b) [aliphatic-aromatic copolyester], the water content of which is less than about 5% by weight, preferably is less than about 1 wt.% Based on the total weight of the polymer blend A, and then using the polymer blend A and admixing the
• polymer blend A is prepared in an extruder and used as granules in the subsequent step.
• polymer blend A can also be a finished, commercially available polymer blend, such as the under the
• the water content of the polymer composition is adjusted to less than 3% by weight, more preferably less than 1.5% by weight, and most preferably less than 1% by weight, based on the total composition.
• Water contents given here refer to the material leaving the extruder.
• a sample of melted extrudate is collected at the nozzle exit on exit from the extruder in a closable vessel and this hermetically sealed. It is important to ensure that the vessel is filled as completely as possible with extrudate, so that the inclusion of air in the vessel is kept as low as possible. After cooling the closed vessel, this is opened, taken a sample and the water content determined by Karl Fischer titration.
• the water content is adjusted by drying during homogenization. The drying process, for example, by degassing the Mixture or, the melt, expediently by removing steam during homogenization or extrusion, carried out.
• the inventive method provides that the mixture is homogenized. Homogenization can be carried out by any measures known to those skilled in the art of plastics engineering. Preferably, this is done
• shear forces act on the mixture during homogenization.
• the mixture is heated during the homogenization (for example in the extruder), preferably to a temperature of 90 to 250 ° C., in particular 130 to 220 ° C.
• the polymer compositions according to the invention are suitable for the
• compositions are suitable for various purposes.
• the compositions are suitable for various purposes.
• the compositions are suitable for various purposes.
• the compositions are suitable for various purposes.
• the invention also relates to moldings, films and fibers produced from the polymer compositions according to the invention.
• Inventive films may be blown, flat or cast films.
• Preferred film thicknesses for blown films according to the invention are from 12 to 100 ⁇ m, for flat films of 150 to 500 ⁇ m according to the invention and from 10 to 500 ⁇ m for cast films according to the invention. The principle of the invention will be explained in more detail below with reference to the single FIGURE (FIG. 1).
• Fig. 1 shows a comparison of the increase in enthalpies of fusion determined from the melting peaks of the DSC charts of films of formulations E and F at different times.
• Exemplary embodiments used were the following materials: polylactic acid, PLA (INGEO 2003D, NATUREWORKS); Poly (butylene adipate-co-terephthalate), PBAT (ECOFLEX F blend C 1201, BASF); Poly (hydroxybutyrate-co-hexanoate), PHBH
• twin-screw extruder of the type Werner & Pseideriderer
• the mechanical properties of the films were determined after a storage time of 24 h at room temperature and ambient atmosphere as follows: ab.4: M echanical properties of films after 24 h
• Example 1 Noticeable in the results of Example 1 (see Table 4) is in particular the low dielectric strength (specific dart drop) and the compared to
• the mechanical properties of the film were determined after a storage time of 24 h at room temperature and ambient atmosphere as follows:
• twin-screw extruder of the type Werner & Pseideriderer
• the mechanical properties of the film were determined after a storage time of 24 h at room temperature and ambient atmosphere as follows:
• Example 14 The results summarized in Table 14 show, compared with Comparative Example 1, a significantly increased impact strength (specific dart drop) and a higher tensile strength in the extrusion direction (MD). Compared with Example 2, there is an increased dielectric strength (specific dart drop) and a significantly increased tensile strength, especially in the direction of extrusion (MD). At the same time, the values for elongation at break and tear propagation resistance are reduced. Obviously, certain mechanical properties can be modified by adding small amounts of an epoxide group-containing copolymer.
• Example 4 Example 4:
• SHIMADZU examined. The samples were each heated from 20 ° C to 220 ° C at a heating rate of 10 ° C / minute.
• Example 3 Under identical conditions as in Example 3, the granules E and F were then processed into blown films with a film thickness of 22 ⁇ each.
• DSC diagrams were measured under the conditions mentioned above for films of formulations E [with PLA) and F (without PLA) immediately after the production of the films, 24 hours after the production of the films and 168 hours after the production of the films. Subsequently, in each diagram, the area of the melting peak was determined by integration. This area corresponds to the
• Post-crystallization in polymer compositions according to the invention by the addition of PLA is reduced compared to polymer compositions without PLA.

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